Semiconductor wafer for epitaxially grown devices having a sub-surface getter region

ABSTRACT

In a semiconductor wafer according to this invention, an epitaxial layer is formed on the surface of a semiconductor substrate, a second element which is not the same but homologous as a first element constituting the semiconductor substrate is present to have a peak concentration on the semiconductor substrate side rather than the surface, and this peak concentration is 1×10 16  atoms/cm 3  or more.

This application is a continuation of application Ser. No. 08/465,750filed Jun. 6, 1995, now abandoned, which is a divisional application ofSer. No. 08/216,052 filed Mar. 21, 1994, now abandoned.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a semiconductor wafer for forming asemiconductor device and, more particularly, a solid stage imagingdevice and a method of manufacturing the semiconductor wafer.

2. Description of the Prior Art

As a semiconductor wafer for forming a semiconductor device, a CZsubstrate grown by a CZ method, an MCZ substrate grown by an MCZ method,an epitaxial wafer obtained by forming an epitaxial layer on the surfaceof the CZ or MCZ substrate, or the like has been conventionally used.

On the other hand, although the step of forming a semiconductor deviceis performed in an ultra clean room of class 100 or less, thesemiconductor substrate cannot be completely prevented from beingcontaminated by impurities from gases, water, and apparatus formanufacturing a semiconductor device and the like. In addition, the doseof impurity implanted into the semiconductor wafer in the step offorming an epitaxial layer on the surface of the semiconductor substrateis larger than the dose of impurity implanted into the semiconductorwafer in the step of forming a semiconductor device.

When an impurity or crystal defects are present in the active region ofthe semiconductor wafer, the quality and characteristics of thesemiconductor device are considerably degraded. In addition, when theimpurity and crystal defects are present in the semiconductor wafer, thesemiconductor wafer is easily damaged by radiation such as α rays, andthe quality and characteristics of the semiconductor device are furtherdegraded by this damage.

In order to remove the impurity and crystal defects from the activeregion, intrinsic gettering (IG) or extrinsic gettering (EG) has beenconventionally performed. FIGS. 1 and 2 show the characteristics of asemiconductor device formed on an epitaxial wafer subjected to theseprocesses described above.

In order to obtain the results shown in FIGS. 1 and 2, epitaxial layerswere simultaneously formed on a CZ substrate which was not subjected togettering, a CZ substrate which was subjected to EG and a CZ substratewhich was subjected to IG, respectively. In this case, the EG wasperformed such that a polysilicon film having a thickness of 1.5 μm wasformed on the lower surface of the CZ substrate by a CVD method at atemperature of 620° C. The IG was performed such that oxygen wasprecipitated by sequentially performing annealing at 1,100° C. for 1.5hours, annealing at 650° C. for 10 hours and annealing at 1,050° C. for2 hours for the CZ substrate to form crystal defects inside the CZsubstrate.

A MOS capacitor having a gate electrode consisting of an Al film and agate insulating film consisting of an SiO₂ film having a thickness of 20nm and a CCD imaging device were formed on each of these epitaxialwafers. FIG. 1 shows a generation life time which is obtained by a C-tmethod using the MOS capacitor and represented as a value normalizedsuch that a measurement value of a CZ substrate is set to be 1. FIG. 2shows the number of white defects of each CCD imaging device representedas a value normalized such that a measurement value of an MCZ substrateis set to be 1. Note that these white defects are equivalent to darkcurrents caused by impurities or the like.

However, as is apparent from FIGS. 1 and 2, even when the EG or IG isperformed for an epitaxial wafer, the generation life time of theepitaxial wafer is almost equal to that of a CZ substrate. The number ofwhite defects of the epitaxial wafer cannot be reduced to that of an MCZsubstrate. On the other hand, in the CZ or MCZ substrate, defects arepresent in not only the substrate but also the gate insulating filmformed on the surface of the substrate, and current leakage caused by adecrease in breakdown voltage of the gate insulating film or an increasein interface state causes a transfer failure or the like in the CCDimaging device.

SUMMARY OF THE INVENTION

In a semiconductor wafer according to the present invention, a secondelement present in a semiconductor substrate at a peak concentration of1×10¹⁶ atoms/cm³ or more accelerates oxygen precipitation to formcrystal defects at a high density in the semiconductor substrate, andthe crystal defects serve as a gettering site. In addition, since thecovalent bonding radius of a first element constituting thesemiconductor substrate is different from that of the second elementpresent in the semiconductor substrate, stress is generated, and thisstress itself serves as a gettering site.

For this reason, impurities and crystal defects which are originallypresent in the semiconductor substrate or impurities and crystal defectswhich are respectively implanted and formed in the semiconductorsubstrate when the epitaxial layer is formed and then when asemiconductor device such as a solid state imaging device is formed arestrongly gettered, and a gettering capability is kept for a long time.

In addition, since the second element has a peak concentration on thesemiconductor substrate side rather than the surface of thesemiconductor substrate, the crystallinity of the surface is rarelydegraded, and the crystallinity of an epitaxial layer formed on thesurface is rarely degraded. Therefore, a semiconductor device which isexcellent in quality and characteristics, and more particularly, a solidstate imaging device having a small number of white defects can beformed.

In a method of manufacturing a semiconductor wafer according to thepresent invention, since an epitaxial layer is formed on the surface ofa semiconductor substrate including a getter region, there can beprovided a semiconductor wafer capable of strongly gettering an impurityand crystal defects which are originally present in a semiconductorsubstrate or an impurity and crystal defects which are respectivelyimplanted and formed in the step of forming an epitaxial layer and thenin the step of forming a semiconductor device, and keeping a getteringcapability for a long time. Therefore, the semiconductor wafer on whicha semiconductor device which is excellent in quality and characteristicscan be formed can be manufactured.

In another method of manufacturing a semiconductor wafer according tothe present invention, a second element ion-implanted into asemiconductor substrate accelerates oxygen precipitation to form crystaldefects at a high density in the semiconductor substrate, and thesecrystal defects serve as a gettering site. In addition, since thecovalent bonding radius of the first element constituting thesemiconductor substrate is different from that of the second elemention-implanted into the semiconductor substrate, stress is generated, andthis stress itself serves as a gettering site.

For this reason, there can be provided a semiconductor wafer capable ofstrongly gettering an impurity and crystal defects which are originallypresent in a semiconductor substrate or an impurity and crystal defectswhich are respectively implanted and formed in the step of forming anepitaxial layer and then in the step of forming a semiconductor device,and keeping a gettering capability for a long time. Therefore, thesemiconductor wafer on which a semiconductor device which is excellentin quality and characteristics can be formed can be manufactured.

In still another method of manufacturing a semiconductor wafer accordingto the present invention, since the dose of a second element is 5×10¹³ions/cm² or more, formation of high-density crystal defects and stressgeneration performed by ion-implanting the second element can besatisfactorily performed, and a semiconductor wafer having a highgettering capability can be manufactured. In addition, since the dose ofthe second element is 5×10¹⁵ ions/cm² or less, the crystallinity of thesurface of the semiconductor substrate is rarely degraded, and thecrystallinity of an epitaxial layer formed on the surface is rarelydegraded. Therefore, a semiconductor wafer on which a semiconductordevice which is excellent in quality and characteristics can be formedcan be manufactured.

In still another method of manufacturing a semiconductor wafer accordingto the present invention, since the cooling step or the like forincreasing a gettering effect is performed when an epitaxial layer isformed, a semiconductor wafer having a gettering capability higher thanthat of a semiconductor wafer in which a second element is onlyion-implanted can be manufactured. Therefore, a semiconductor wafer onwhich a semiconductor device which is excellent in quality andcharacteristics can be formed can be manufactured.

In still another method of manufacturing a semiconductor wafer accordingto the present invention, oxygen precipitation is more accelerated whena second element is ion-implanted into a semiconductor substrate so thatcrystal defects can be formed at a high density. For this reason, asemiconductor wafer having a higher gettering capability can bemanufactured. Therefore, a semiconductor wafer on which a semiconductordevice which is excellent in quality and characteristics, moreparticularly, a solid state imaging device having a small number ofwhite defects, can be formed.

In still another method of manufacturing a semiconductor wafer accordingto the present invention, there can be provided a semiconductorsubstrate in which the number of point defects and the number ofclusters of the point defects formed during crystal growth areoriginally small, and, even when an impurity and crystal defects arepresent, the impurity and the crystal defects can be strongly getteredby precipitated oxygen. Therefore, a semiconductor wafer on which asemiconductor device which is excellent in quality and characteristics,more particularly, a solid state imaging device having a small number ofwhite damage defects, can be formed can be manufactured.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph showing the relationship between the type of asemiconductor substrate and a generation life time;

FIG. 2 is a graph showing the relationship between the type of thesemiconductor substrate and the number of white defects;

FIGS. 3A to 3C are views sequentially showing the steps in manufacturinga semiconductor wafer according to the first embodiment of the presentinvention;

FIG. 4 is a graph showing the relationship between the dose of carbonand the number of white defects;

FIG. 5 is a graph showing the relationship between the oxygenconcentration of an Si wafer and the number of white defects; and

FIG. 6 is a graph showing the relationship between an Si crystal growthrate, the yield of SiO₂ breakdown strength and the number of whitedefects.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The first and second embodiments of the present invention will bedescribed below with reference to FIGS. 1 to 6. FIGS. 3A to 3C show thefirst embodiment. According to the first embodiment, as shown in FIG.3A, a CZ substrate 11 which is an Si substrate grown by a CZ method isprovided. In this CZ substrate 11, the surface is set to be a mirrorsurface 12, a resistivity is set to be 1 to 10 Ω·cm, and an oxygenconcentration is set to be 1.5×10¹⁸ atoms/cm³. This CZ substrate 11 iswashed with an aqueous NH₄ OH/H₂ O₂ solution and then washed with anaqueous HCl/H₂ O₂ solution.

The CZ substrate 11 is dry-oxidized at a temperature of 1,000° C., and,as shown in FIG. 3B, an SiO₂ film 13 having a thickness of about 20 nmis formed on the mirror surface 12. Carbon 14 is ion-implanted from themirror surface 12 into the CZ substrate 11 through the SiO₂ film 13 atan acceleration energy of 800 keV and a dose of 1×10¹⁴ ions/cm². At thistime the projected range of the carbon 14 is about 1.3 μm, and the peakconcentration of the carbon 14 is about 1×10¹⁸ atoms/cm³.

The resultant structure is annealed in an N₂ atmosphere at 1,000° C. for10 minutes. As a result, as shown in FIG. 3C, carbon-implanted region 15having a peak concentration at a position deeper than the mirror surface12 of the CZ substrate 11 is formed. The peak concentration of thecarbon 14 in the carbon implanted region 15 is set to be 1×10¹⁶atoms/cm³ or more.

Thereafter, the SiO₂ film 13 is removed by an aqueous HF/NH₄ F solution.An Si epitaxial layer 16 having a resistivity of about 20 to 30 Ω·cm anda thickness of about 10 μm is grown on the mirror surface 12 at atemperature of about 1,150° C. using SiHCl₃ gas, thereby completing anepitaxial wafer 17.

The position of the peak concentration of the carbon 14 in the carbonimplanted region 15 is located at a position deeper than the mirrorsurface 12 because of the following reason. That is, when the positionof the peak concentration is located on the mirror surface 12, thecrystallinity of the mirror surface 12 is degraded, and thecrystallinity of the Si epitaxial layer 16 grown on mirror surface 12 isdegraded. In addition, ling is performed in an N₂ atmosphere after theion implantation is performed because of the following reason. That is,since the Si epitaxial layer 16 is grown on the mirror surface 12 later,the crystallinity of the CZ substrate 11 near the mirror surface 12converted into an amorphous state by the ion implantation is restored.

In addition, the SiO₂ film 13 is formed on the mirror surface 2 becauseof the following reason. That is, when carbon 14 is ion-implanted,channeling is prevented, and the surface 12 is prevented from beingsputtered. SiO₂ film 13 and annealing in an N₂ atmosphere are notnecessarily required depending on an acceleration or dose at which thecarbon 14 is ion-implanted.

FIGS. 1 and 2 show also values measured by using the epitaxial wafer 17of the first embodiment. The CZ substrate for forming a conventionalepitaxial wafer shown in FIGS. 1 and 2 and the CZ substrate 11 forforming the epitaxial wafer 17 of the first embodiment have the samespecifications. As is apparent from FIGS. 1 and 2, the generation lifetime of the CZ substrate 11 of this embodiment is about 1.4 times thatof the conventional CZ substrate, the number of white defects of the CZsubstrate 11 is about 1/2 that of the conventional CZ substrate. Thatis, in the epitaxial wafer 17 even when a semiconductor device isformed, a gettering capability effectively functions.

Note that, in the first embodiment, although the carbon 14 ision-implanted into the CZ substrate 11 at an acceleration energy of 800keV and a dose of 1×10¹⁴ ions/cm², the relationship between the dose ofthe carbon 14 and the number of white defects of a CCD imaging deviceformed on the epitaxial wafer 17, obtained when only the dose of theabove conditions is variously changed, is shown in FIG. 4.

FIG. 4, as in FIG. 2, shows a value normalized such that the number ofwhite damage defects of a CCD imaging device formed on the MCZ substrateis set to be 1. Although FIG. 2 is a logarithmic graph, FIG. 4 is alinear graph. As is apparent from FIG. 4, although the number of whitedefects of the CCD imaging device becomes smaller than that of the CCDimaging device on the MCZ substrate when the carbon 14 is onlyion-implanted, when the dose is set to be 5×10¹³ ions/cm² or more, thenumber of white defects is particularly small, and a large getteringeffect can be obtained by ion implantation of the carbon 14.

However when the dose exceeds 5×10¹⁵ ions/cm², the crystallinity of themirror surface 12 of the CZ substrate 11 is degraded, and thecrystallinity of the Si epitaxial layer 16 grown on the mirror surface12 is degraded. Therefore, the dose of the carbon 14 preferably fallswithin a range of 5×10¹³ to 5×10¹⁵ ions/cm².

In the first embodiment described above, although the carbon 14 ision-implanted at an acceleration energy of 800 keV, even when thisacceleration energy is set to be 400 keV, a gettering effect equal tothat obtained by the acceleration energy of 800 keV may be obtained byion implantation of the carbon 14; even when the acceleration energy isset to be 200 keV, a gettering effect equal to that obtained at theacceleration energy of 800 keV may be obtained by ion implantation ofthe carbon 14.

Therefore, when the carbon 14 is ion-implanted at a low accelerationenergy, a generally used high-current ion implantation equipment can beused, and C⁺ capable of obtaining a current ten times a current obtainedb C²⁺ can be used. For this reason, the throughput of he semiconductorwafer implanted by 200 keV can be about 10 times that of thesemiconductor wafer implanted by 800 keV.

When the acceleration energies are set to be 400 keV and 200 keV, theprojected range of the carbon 14 are about 0.75 μm and about 0.40 μm,respectively. In either case, as in the case wherein the accelerationenergy is set to b 800 keV, the carbon-implanted region 15 having a peakconcentration at a position deeper than the mirror surface 12 of the CZsubstrate 11 can be formed.

In the first embodiment, although the Si epitaxial layer 16 is grown onthe mirror surface 12 of the CZ substrate if at a time, the steps ofgrowing the Si epitaxial layer 16 at an epitaxial growth temperature tohave a predetermined thickness and temporarily cooling the CZ substrate11 to the temperature which is 1/2 the epitaxial growth temperature orless may be repeated two or more times, thereby forming the Si epitaxiallayer 16 having a desired thickness.

In this manner, since the CZ substrate 11 receives the heat hysteresistwo or more times when the Si epitaxial layer 16 is formed, crystaldefects formed in the CZ substrate 11 by ion implantation of the carbon14 are more grown, and the gettering capability of the epitaxial wafer17 is more improved.

In the first embodiment, although only ion implantation of the carbon 14is performed to improve the gettering capability of the epitaxial wafer17, when EG performed by forming a polysilicon film or aphospho-silicate glass film on the lower surface of the CZ substrate 11,the gettering capability can be more improved.

In the first embodiment, although only the carbon 14 is ion-implantedinto the CZ substrate 11 which is an Si substrate, Ge, Sn, Pb or thelike which is a Group IV element may be ion-implanted into the CZsubstrate 11 in place of the carbon 14, and an element other than aGroup IV element may be ion-implanted into the CZ substrate 11 togetherwith the Group IV element such as the carbon 14. In addition, accordingto the first embodiment, although the CZ substrate 11 which is an Sisubstrate is used, an MCZ substrate may be used as the Si substrate anda substrate other than an Si substrate may be used. When the substrateother than the Si substrate, a least an element which is not the samebut homologous as the element constituting this substrate andelectrically neutral is ion-implanted into the substrate.

In the first embodiment, although the Si epitaxial layer 16 grown usingSiHCl₃, SiCl₄, SiH₂ Cl₂, SiH₃ Cl or SiH₄ may be used in place of SiHCl₃.In particular, it known that the characteristics of the semiconductorare more improved using SiH₄.

The embodiment will be described below. According the second embodiment,an Si crystal growth rate obtained by an MCZ method was set to be 0.5mm/min, and an Si wafer having an oxygen concentration of 1×10¹⁸atoms/cm³, the surface as a mirror surface and a resistivity of about 20Ω·cm was formed. A MOS capacitor having a gate electrode consisting ofan Al film and a gate insulating film consisting of an SiO₂ film havinga thickness of 20 nm and a CCD imaging device were formed on the Siwafer.

When the Si wafer manufactured according to the second embodiment iscompared with an Si wafer manufactured according to the prior art, theyield of SiO₂ breakdown strength of the MOS capacitor according to thesecond embodiment is increased to about 4 times that of the MOScapacitor according to the prior art, and the number of white defects ofthe CCD imaging device according to the second embodiment is reduced to1/5 or less that of the CCD imaging device according to the prior art.Note that, although the Si crystal is grown by the MCZ method in thesecond embodiment, when the Si crystal is grown by a CZ method, the sameeffect as described above can be expected.

FIG. 5 shows the relationship between the oxygen concentration of the Siwafer and the number of white defects of the CCD imaging device formedon the Si wafer, obtained when the oxygen concentration of the Si waferis variously changed. As is apparent from FIG. 5, the number of whitedefects is stably kept small when the oxygen concentration is set to be8×10¹⁷ atoms/cm³ or more. This may occur because an impurity or crystaldefects are gettered by an IG effect naturally caused in the step offorming the CCD imaging device.

FIG. 6 shows the relationship between the Si crystal growth rate, theyield of SiO₂ breakdown strength of the MOS capacitor formed on the Siwafer and the number of white defects of the CCD imaging device,obtained when the Si crystal growth rate is variously changed the oxygenconcentration of the Si wafer is fixed 9×10¹⁷ atoms/cm³. As is apparentfrom FIG. 6, when the growth rate is 1 mm/min or less, the yield of SiO₂breakdown strength of the SiO₂ film and the number of white defects havepreferable values. This may occur because the number of point defectsand the number of clusters of the point defects formed in growing thecrystal are small due to a low growth rate.

Therefore, when a CCD imaging device is formed on the Si wafer describedabove, not only the number of white defects is small, a transfer failureor the like caused by a decrease in breakdown voltage of the gateinsulating film rarely occurs. Note that about 1.5 mm/min has beenconventionally employed as the Si crystal growth speed in considerationof productivity.

What is claimed is:
 1. In combination, a solid state imaging device anda semiconductor wafer, including:a semiconductor wafer comprising: asemiconductor substrate comprised of silicon and having a surface onwhich electronic devices will be formed, said substrate containing anion-implanted getter region beneath and spaced from said surface;wherein said implanted ion is carbon implanted through a silicon dioxidelayer formed on said surface, said surface re-crystallized by annealingafter removal of the silicon dioxide layer; and a solid state imagingdevice formed on the recrystallized surface.
 2. A combination of asemiconductor wafer and a solid state imaging device according to claim1, wherein said carbon in said getter region has a peak concentration of1×10¹⁶ atoms/cm³ or more.
 3. A combination of a semiconductor wafer anda solid state imaging device according to claim 1, wherein said carbonin said getter region is implanted at a dose of 5×10¹³ to 5×10¹⁵ions/cm².
 4. A combination of a semiconductor wafer and a solid stateimaging device according to claim 1, wherein said semiconductorsubstrate contains oxygen at a concentration of its solubility limit ormore.
 5. A combination of a semiconductor wafer and a solid stateimaging device according to claim 1, wherein said oxygen concentrationis controlled to 8×10¹⁷ atoms/cm³ or more.
 6. A combination of asemiconductor wafer and a solid state imaging device according to claim1, wherein said carbon is implanted through said surface for formingelectronic devices at an acceleration energy of about 200 keV to about800 keV.
 7. A combination of a semiconductor wafer and a solid stateimaging device according to claim 1, wherein said carbon is implantedthrough said surface for forming electronic devices at an accelerationenergy of about 800 keV and a dose of about 1×10¹⁴ ions/cm².
 8. Acombination of a semiconductor wafer and a solid state imaging deviceaccording to claim 1, wherein said silicon is formed by the Czochralski(CZ) method with a resistivity of about 1 to 10 ohms-cm and an oxygenconcentration of about 1.5×10¹⁸ atoms/cm³.
 9. A silicon-containing waferhaving a surface for growing an epitaxial layer thereon, said wafercomprising:a silicon substrate having an initial oxygen concentration ofat least 8×10¹⁷ atoms/cm³ ; a getter site region formed in said siliconsubstrate beneath and spaced from said surface for growing an epitaxiallayer, said getter sites created by ion-implantation of ions selectedfrom the Group IV elements of C, Ge, Sn, Pb and ion-implanted into saidgetter site region through a silicon dioxide layer formed on saidsurface for growing an epitaxial layer, the silicon dioxide layer ofsufficient thickness to avoid sputtering onto said surface for growingan epitaxial layer by the ion-implantation, said surface for growing anepitaxial layer re-crystallized subsequent to ion-implantation byannealing after removal of the silicon dioxide layer.
 10. Thesilicon-containing wafer of claim 9, wherein said silicon substrate isformed by the Czochralski (CZ) method with a crystal growth rate of 1.0mm/min or less.
 11. The silicon-containing wafer of claim 9, whereinsaid initial oxygen concentration is 8×10¹⁷ atoms/cm³ and said siliconsubstrate has an initial resistivity of about 1 to 10 ohms-cm.
 12. Thesilicon-containing wafer of claim 9, wherein said implanted ion iscarbon implanted at a dose of between about 5×10¹³ ions/cm² and about5×10¹⁵ ions/cm².
 13. The silicon-containing wafer of claim 9, whereinsaid implanted ion is carbon implanted at a dose of about 1×10¹⁴ions/cm².
 14. The silicon-containing wafer of claim 12, wherein saidimplanted ions are implanted at an acceleration energy between about 200keV and 800 keV.
 15. The silicon-containing wafer of claim 11, whereinsaid carbon-implanted getter region has a peak concentration of about1×10¹⁶ atoms/cm³ at a position spaced from and beneath said surface forgrowing an epitaxial layer.
 16. The silicon-containing wafer of claim 9,further comprising at least one electronic device epitaxially formed onthe surface for growing an epitaxial layer.
 17. The silicon-containingwafer of claim 16, further comprising a charged-coupled imaging deviceepitaxially formed on the surface for growing an epitaxial layer.